JP2005029726A - Non-resonating multiple photon absorption material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a highly efficient non-resonating two photon absorption material applicable to three-dimensional stereo lithographic composition, three-dimensional display, three-dimensional optical recording medium, etc., by making functions such as polymerization, reaction, coloring, refractive index modulation, light emission, etc., to develop at high efficiency. <P>SOLUTION: This non-resonating multiple photon absorption material includes a non-resonating multiple photon absorption compound which functions at high efficiency as a sensitizing coloring material or a light emitting coloring material by non-resonating multiple photon absorption. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a material that exhibits a nonlinear optical effect, and in particular, uses a two-photon absorption compound having a large non-resonant two-photon absorption cross-section and its excitation energy to efficiently perform polymerization, reaction, color development, refractive index modulation, light emission, and the like. The present invention relates to a two-photon absorption material that can be used for the following. The present invention also relates to a three-dimensional stereolithography composition using these materials, a three-dimensional display, and a three-dimensional optical recording medium.

  In general, the nonlinear optical effect is a non-linear optical response proportional to the square of the applied photoelectric field, the third power or more, and a second-order nonlinear optical effect proportional to the square of the applied photoelectric field. For example, second harmonic generation (SHG), optical rectification, photorefractive effect, Pockels effect, parametric amplification, parametric oscillation, optical sum frequency mixing, optical difference frequency mixing, and the like are known. The third-order nonlinear optical effect proportional to the cube of the applied photoelectric field includes third harmonic generation (THG), optical Kerr effect, self-induced refractive index change, two-photon absorption, and the like.

  Many inorganic materials have been found so far as nonlinear optical materials exhibiting these nonlinear optical effects. However, inorganic materials are very difficult to put into practical use because so-called molecular design for optimizing desired nonlinear optical characteristics and various physical properties necessary for device fabrication is difficult. On the other hand, organic compounds can be optimized not only for the desired nonlinear optical properties by molecular design, but also for other physical properties, so they are highly practical and attract attention as promising nonlinear optical materials. Collecting.

  In recent years, the third-order nonlinear optical effect has attracted attention among the nonlinear optical characteristics of organic compounds, and among these, non-resonant two-photon absorption has attracted attention. Two-photon absorption is a phenomenon in which a compound is excited by simultaneously absorbing two photons, and the case where two-photon absorption occurs in an energy region where there is no (linear) absorption band of the compound is called non-resonant two-photon absorption. . In the following description, two-photon absorption refers to non-resonant two-photon absorption even if not specified.

By the way, the efficiency of non-resonant two-photon absorption is proportional to the square of the applied photoelectric field (square characteristic of two-photon absorption). For this reason, when a two-dimensional plane is irradiated with a laser, two-photon absorption occurs only at a position where the electric field strength is high in the central portion of the laser spot, and two-photon absorption is completely absent in a portion where the electric field strength is weak in the peripheral portion. Does not happen. On the other hand, in the three-dimensional space, non-resonant two-photon absorption occurs only in a region where the electric field strength at the focal point where the laser light is collected by the lens is large, and the two-photon absorption is completely absent in the region outside the focal point. Does not happen. Compared with linear absorption where excitation occurs at all positions in proportion to the intensity of the applied photoelectric field, non-resonant two-photon absorption results in excitation at only one point inside the space due to this square characteristic. , The spatial resolution is significantly improved.
Usually, when inducing non-resonant two-photon absorption, a short-pulse laser in the near-infrared region, which is longer than the wavelength region in which the (linear) absorption band of the compound exists and does not have absorption, is often used. The so-called transparent near-infrared light is used, so that the excitation light can reach the inside of the sample without being absorbed or scattered, and because of the square characteristic of non-resonant two-photon absorption, one point inside the sample has an extremely high spatial resolution. Can be excited.

Therefore, if polymerization, reaction, color development, refractive index modulation, light emission, etc. can be caused using excitation energy obtained by non-resonant two-photon absorption, they can be caused in any place in the three-dimensional space, A composition for three-dimensional stereolithography, a so-called volume type three-dimensional display, a three-dimensional optical recording medium, and the like can be provided.
Further, it can be applied to a wavelength conversion device using two-photon contrast imaging, two-photon photodynamic therapy (PDT), or up-conversion lasing of a living tissue.

  The problem in application of the non-resonant two-photon absorption compound to the above-described material is that the known non-resonant two-photon absorption compound has a small two-photon absorption efficiency (cross-sectional area), so that a very strong laser is applied for a long time. Irradiation is necessary, which causes damage to materials and living bodies, hinders improvement in writing (transfer) speed and polymerization speed, and hinders downsizing and cost reduction of lasers, which is a big problem in practical use. Therefore, it functions as a sensitizing dye that can cause writing, polymerization, light emission, etc. in a short time even with a relatively weak laser, and functions as a highly efficient non-resonant two-photon absorption compound or luminescent dye. Development of an efficient two-photon absorption compound is strongly desired.

  Here, WO9709043 [Patent Document 1] describes various application examples using two-photon emission of a stilbazolium compound having a specific structure. However, the two-photon emission efficiency of the stilbazolium derivative is low, and the performance is still not sufficient for practical use.

  On the other hand, a method has been disclosed in which a photochromic material is used as a non-resonant two-photon absorption material and a color reaction or fluorescence emission is imparted by two-photon absorption (Korotif, Nikolai Eye et al., Special Table 2001-522119 [Patent Document] 2], Arsenov, U "Radimir et al., JP-T-2001-508221 [Patent Document 3]), no two-photon absorption material is presented, and two-photon absorption photochromic is presented abstractly. Examples of compounds are two-photon absorption compounds that have extremely low non-resonant two-photon absorption efficiency as far as we have investigated, and are far from materials that can efficiently develop or emit light by non-resonant two-photon absorption.

  Examples of two-photon photopolymerization using sensitization by a non-resonant two-photon absorption compound and applied to optical modeling are described in the following documents (BH Cumpston et al., Nature. 1999). Year, 398, 51 pages [Non-Patent Document 1], KD Belfield et al., J. Phys. Org. Chem., 2000, 13, page 837 [Non-Patent Document 2], C. Li. et al., Chem. Phys. Lett., 2001, 340, 444 [Non-Patent Document 3], KD Belfield et al., J. Am. Chem. Soc., 2000, 122, 1217 [Non-patent document 4], S. Maruo et al., Opt. Lett., 1997, 22, p. 132 [Non-patent document 5]).

  However, even in these examples, the non-resonant two-photon absorption cross-sectional area of the two-photon absorption compound is small, and the sensitization function of the two-photon absorption compound is insufficient, resulting in poor polymerization efficiency. In order to do so, it was necessary to irradiate a strong laser for a long time, which was a practical problem.

As described above, the known materials have many practical problems due to the small non-resonant two-photon absorption efficiency (cross-sectional area) of the two-photon absorption compound, low luminous efficiency, and low sensitization efficiency. As described above, development of a non-resonant two-photon absorption compound that functions as a sensitizing dye and has high efficiency or a non-resonant two-photon absorption compound that functions as a light-emitting dye and has high efficiency is strongly desired.
B. H. Cumpston et al. , Nature. 1999, 398, 51 K. D. Belfield et al. , J .; Phys. Org. Chem. 2000, vol. 13, p. 837 C. Li et al. , Chem. Phys. Lett. 2001, 340, 444 K. D. Belfield et al. , J .; Am. Chem. Soc. 2000, 122, 1217 S. Maruo et al. , Opt. Lett. 1997, Vol. 22, p. 132 International Publication No. 9709043 Pamphlet Special table 2001-522119 gazette Special table 2001-508221 gazette

As described above, if a material capable of performing polymerization, reaction, color development, refractive index modulation, light emission, or the like with high efficiency using excitation energy obtained by non-resonant two-photon absorption can be provided, any arbitrary three-dimensional space can be provided. It is possible to cause them to occur at extremely high spatial resolution, and to provide a three-dimensional stereolithography composition, a so-called volume type three-dimensional display, a three-dimensional optical recording medium, and the like.
In particular, for use in a three-dimensional display or a three-dimensional optical recording medium, two-photon absorption is performed with high sensitivity and the excitation energy is used for display or reproduction with a high writing speed and a high S / N ratio. Therefore, development of a two-photon absorption compound that can emit light or sensitize with high efficiency is essential. However, currently available two-photon absorption compounds have low non-resonant two-photon absorption efficiency and low emission efficiency and sensitization efficiency.
Therefore, an object of the present invention is to increase the application to three-dimensional stereolithography compositions, three-dimensional displays, three-dimensional optical recording media, etc. by developing functions such as polymerization, reaction, color development, refractive index modulation, and light emission. An object of the present invention is to provide a non-resonant multiphoton absorbing material containing a highly efficient nonresonant multiphoton absorbing compound that functions as a dye or a highly efficient nonresonant multiphoton absorbing compound that functions as a luminescent dye.

As a result of intensive studies by the inventors, the compound functions as a sensitizing dye and absorbs non-resonant two-photons with high efficiency, that is, a compound having a large non-resonant two-photon absorption cross-section, and functions as a luminescent dye, and The inventors have found a compound having a large resonance two-photon absorption cross section.
Therefore, the above object of the present invention has been achieved by the following means.

(1) A high-efficiency non-resonant multi-photon absorption compound, which functions as a sensitizing dye with high efficiency by non-resonant multi-photon absorption.
(2) A nonresonant multiphoton absorption compound characterized in that, in (1), the sensitization functions as a sensitizing dye according to (1) by an energy transfer mechanism or an electron transfer mechanism.
(3) In (1) or (2), the non-resonant multi-photon absorption compound absorbs multi-photons non-resonantly, so that any of polymerization, reaction, color development, refractive index modulation, and light emission is highly efficient. A nonresonant multiphoton absorption compound which functions as a sensitizing dye according to (1) or (2), which is sensitized.
(4) In (3), the non-resonant multiphoton absorption compound sensitizes any of color development, refractive index modulation, and light emission with high efficiency by absorbing multiphotons nonresonantly, (3) A nonresonant multiphoton absorption compound characterized by functioning as a sensitizing dye.
(5) In (1) to (4), the non-resonant multiphoton absorption compound is other than a phenylene vinylene dye, a diarylethene dye, a spiropyran dye, a fulgide dye, a fluorene dye, a xanthene dye, a coumarin dye, or a perylene dye. A non-resonant multiphoton absorption compound which functions as the sensitizing dye according to any one of (1) to (4).
(6) In (1) to (5), the non-resonant multiphoton absorption compound is a cyanine dye, hemicyanine dye, streptocyanine dye, styryl dye, pyrylium dye, merocyanine dye, trinuclear merocyanine dye, tetranuclear merocyanine dye, Rhodocyanine dye, complex cyanine dye, complex merocyanine dye, allopolar dye, arylidene dye, oxonol dye, hemioxonol dye, squalium dye, croconium dye, azurenium dye, ketocoumarin dye, styrylcoumarin dye, pyran dye, anthraquinone dye, quinone dye, Triphenylmethane dye, diphenylmethane dye, thioxanthene dye, phenothiazine dye, phenoxazine dye, phenazine dye, azo dye, azomethine dye, indigo dye, polyene dye Acridine dye, acridinone dye, diphenylamine dye, quinacridone dye, quinophthalone dye, porphyrin dye, azaporphyrin dye, chlorophyll dye, phthalocyanine dye, condensed ring aromatic dye, styrenic dye, metallocene dye, metal complex dye, stilbazolium dye A non-resonant multiphoton absorption compound that functions as a sensitizing dye according to (1) to (5).
(7) In (6), the non-resonant multiphoton absorption compound is a cyanine dye, hemicyanine dye, streptocyanine dye, styryl dye, pyrylium dye, merocyanine dye, trinuclear merocyanine dye, tetranuclear merocyanine dye, rhodacyanine dye, complex Cyanine dyes, complex merocyanine dyes, allopolar dyes, arylidene dyes, oxonol dyes, hemioxonol dyes, squalium dyes, croconium dyes, azurenium dyes, ketocoumarin dyes, styrylcoumarin dyes, pyran dyes, anthraquinone dyes, quinone dyes, triphenylmethane dyes , Diphenylmethane dye, thioxanthene dye, phenothiazine dye, phenoxazine dye, phenazine dye, azo dye, azomethine dye, indigo dye, polyene dye, acrylic The dye according to (6), which is any one of a dye, an acridinone dye, a diphenylamine dye, a quinacridone dye, a quinophthalone dye, an azaporphyrin dye, a chlorophyll dye, a phthalocyanine dye, a condensed aromatic dye, a metallocene dye, and a metal complex dye. A nonresonant multiphoton absorption compound characterized by functioning as a dye.
(8) In (1) to (7), the nonresonant multiphoton absorption compound functions as a sensitizing dye described in (1) to (7), which is a nonresonant two-photon absorption compound. Resonant two-photon absorption compound.
(9) The non-resonant two-photon functioning as the sensitizing dye according to any one of (1) to (8), wherein the non-resonant two-photon absorption cross-section is 100 GM or more in (1) to (8) Absorbing compound.
(10) The nonresonant two-photon absorption compound characterized by functioning as a sensitizing dye according to (9), wherein the nonresonant two-photon absorption cross-section is 1000 GM or more in (9).
(11) A nonresonant two-photon absorption compound characterized by functioning as a sensitizing dye according to (9), wherein the nonresonant two-photon absorption cross-section is 10,000 GM or more in (9).
(12) A nonresonant multiphoton absorbing compound which functions as a luminescent dye with high efficiency by nonresonant multiphoton absorption.
(13) (1) to (4), (12) having a nonresonant multiphoton absorption emission area that exceeds the emission area by nonresonant multiphoton absorption of the following compound R-1 in a solution of 10 ⁻⁴ M concentration A nonresonant multiphoton absorption compound which functions as the luminescent dye described.

(14) In (13), the compound R-1 has a nonresonant multiphoton absorption emission area that is 10 times or more the emission area by nonresonant multiphoton absorption of the compound R-1, and functions as a luminescent dye according to (13). A non-resonant multiphoton absorption compound.
(15) In (13), the compound R-1 has a nonresonant multiphoton absorption emission area of 100 times or more of the emission area by nonresonant multiphoton absorption of the compound R-1, and functions as a luminescent dye according to (13). A non-resonant multiphoton absorption compound.
(16) In (12) to (15), the nonresonant multiphoton absorption compound is a phenylene vinylene dye, diarylethene dye, spiropyran dye, fulgide dye, porphyrin dye, styrene dye, fluorene dye, xanthene dye, stilbazolium dye A non-resonant multiphoton absorption compound that functions as a luminescent dye described in (12) to (15).
(17) In (12) to (16), the non-resonant multiphoton absorption compound is a cyanine dye, hemicyanine dye, streptocyanine dye, styryl dye, pyrylium dye, merocyanine dye, trinuclear merocyanine dye, tetranuclear merocyanine dye, Rhodocyanine dye, complex cyanine dye, complex merocyanine dye, allopolar dye, arylidene dye, oxonol dye, hemioxonol dye, squalium dye, croconium dye, azurenium dye, coumarin dye, ketocoumarin dye, styryl coumarin dye, pyran dye, anthraquinone dye, Quinone dye, triphenylmethane dye, diphenylmethane dye, thioxanthene dye, phenothiazine dye, phenoxazine dye, phenazine dye, azo dye, azomethine dye, perylene Dye, phthaloperylene dye, indigo dye, polyene dye, acridine dye, acridinone dye, diphenylamine dye, quinacridone dye, quinophthalone dye, azaporphyrin dye, chlorophyll dye, phthalocyanine dye, fused aromatic dye, metallocene dye, metal complex dye, A nonresonant multiphoton absorption compound that functions as the luminescent dye described in any one of (12) to (16).
(18) In (12) to (17), the nonresonant multiphoton absorbing compound is a nonresonant two-photon absorbing compound, and functions as the luminescent dye described in (12) to (17). Two-photon absorption compound.
(19) The non-resonant two-photon absorption characterized by functioning as a luminescent dye according to (12) to (18), wherein the non-resonant two-photon absorption cross-section is 100 GM or more in (12) to (18) Compound.
(20) The nonresonant two-photon absorption compound characterized by functioning as a luminescent dye according to (19), wherein the nonresonant two-photon absorption cross-section is 1000 GM or more in (19).
(21) The nonresonant two-photon absorption compound characterized by functioning as a luminescent dye according to (19), wherein the nonresonant two-photon absorption cross-section is 10,000 GM or more in (19).
(22) Non-resonant multi-photon absorption induction in which multi-photon absorption is induced by irradiating the non-resonant multi-photon absorption compound according to (1) to (21) with laser light having a wavelength longer than the linear absorption band of the compound Method.
(23) The non-resonant multiphoton absorption compound according to any one of (1) to (21), which is used as a three-dimensional stereolithography composition.
(24) The non-resonant multiphoton absorption compound according to any one of (1) to (21), which is used as a three-dimensional display.
(25) The nonresonant multiphoton absorption compound according to any one of (1) to (21), which is used as a three-dimensional optical recording medium.

  The non-resonant two-photon absorption compound of the present invention can function as a sensitizing dye or a luminescent dye with extremely high efficiency.

  The nonresonant multiphoton absorbing compound functioning as the sensitizing dye of the present invention or the nonresonant multiphoton absorbing compound functioning as the luminescent dye will be described.

  The non-resonant multiphoton absorption compound of the present invention may simultaneously absorb any number of photons of two or more photons in the non-resonance process, but preferably performs non-resonant two-photon absorption.

  The two-photon absorption compound of the present invention is a compound that performs non-resonant two-photon absorption (a phenomenon in which two photons are simultaneously excited in an energy region where no (linear) absorption band of the compound exists).

The non-resonant multiphoton absorption compound of the present invention is preferably an organic compound.
In the present invention, when a specific moiety is referred to as a “group”, unless otherwise specified, it may be substituted with one or more (up to the maximum possible) substituents. It means that it is not necessary. For example, “alkyl group” means a substituted or unsubstituted alkyl group. Moreover, the substituent which can be used for the compound in the present invention may be any substituent regardless of the presence or absence of substitution.
In the present invention, when a specific moiety is referred to as “ring”, or when “group” includes “ring”, it may be monocyclic or condensed unless otherwise specified. May not be substituted.
For example, the “aryl group” may be a phenyl group, a naphthyl group, or a substituted phenyl group.

The non-resonant multiphoton absorption compound of the present invention is more preferably a dye. In addition, a pigment | dye here is a general term with respect to the compound which has a part of absorption in visible region (400-700 nm) or near-infrared region (700-2000 nm).
Any dye may be used in the present invention. For example, cyanine dye, hemicyanine dye, streptocyanine dye, styryl dye, pyrylium dye, merocyanine dye, trinuclear merocyanine dye, tetranuclear merocyanine dye, rhodacyanine dye, complex cyanine dye, Complex merocyanine dye, allopolar dye, arylidene dye, oxonol dye, hemioxonol dye, squalium dye, croconium dye, azurenium dye, coumarin dye, ketocoumarin dye, styrylcoumarin dye, pyran dye, anthraquinone dye, quinone dye, triphenylmethane dye , Diphenylmethane dye, xanthene dye, thioxanthene dye, phenothiazine dye, phenoxazine dye, phenazine dye, azo dye, azo dye Dye, fluorenone dye, diarylethene dye, spiropyran dye, fulgide dye, perylene dye, phthaloperylene dye, indigo dye, polyene dye, acridine dye, diphenylamine dye, quinacridone dye, quinophthalone dye, porphyrin dye, azaporphyrin dye, chlorophyll Dyes, phthalocyanine dyes, condensed aromatic dyes, styrenic dyes, metallocene dyes, metal complex dyes, phenylene vinylene dyes, or stilbazolium dyes are preferred, more preferably cyanine dyes, hemicyanine dyes, streptocyanine dyes, styryl dyes, Pyrylium dye, merocyanine dye, trinuclear merocyanine dye, tetranuclear merocyanine dye, rhodacyanine dye, complex cyanine dye, complex dye Cyanine dyes, allopolar dyes, arylidene dyes, oxonol dyes, hemioxonol dyes, squalium dyes, croconium dyes, azurenium dyes, coumarin dyes, ketocoumarin dyes, styrylcoumarin dyes, pyran dyes, anthraquinone dyes, quinone dyes, triphenylmethane dyes, Diphenylmethane dye, thioxanthene dye, phenothiazine dye, phenoxazine dye, phenazine dye, azo dye, azomethine dye, perylene dye, phthaloperylene dye, indigo dye, polyene dye, acridine dye, acridinone dye, diphenylamine dye, quinacridone dye, quinophthalone dye, Porphyrin dye, azaporphyrin dye, chlorophyll dye, phthalocyanine dye, condensed aromatic dye, styrenic dye, metallocene A dye, a metal complex dye, or a stilbazolium dye, and more preferably a cyanine dye, hemicyanine dye, streptocyanine dye, styryl dye, pyrylium dye, merocyanine dye, trinuclear merocyanine dye, tetranuclear merocyanine dye, rhodacyanine dye, complex cyanine dye , Complex merocyanine dye, allopolar dye, arylidene dye, oxonol dye, hemioxonol dye, squalium dye, croconium dye, azurenium dye, ketocoumarin dye, styrylcoumarin dye, pyran dye, anthraquinone dye, quinone dye, triphenylmethane dye, diphenylmethane Dye, thioxanthene dye, phenothiazine dye, phenoxazine dye, phenazine dye, azo dye, azomethine dye, indigo Element, polyene dye, acridine dye, acridinone dye, diphenylamine dye, quinacridone dye, quinophthalone dye, azaporphyrin dye, chlorophyll dye, phthalocyanine dye, condensed aromatic dye, metallocene dye, or metal complex dye, more preferably Cyanine dye, hemicyanine dye, streptocyanine dye, styryl dye, pyrylium dye, merocyanine dye, arylidene dye, oxonol dye, squalium dye, ketocoumarin dye, styrylcoumarin dye, pyran dye, thioxanthene dye, phenothiazine dye, phenoxazine dye, phenazine A dye, an azo dye, a polyene dye, an azaporphyrin dye, a chlorophyll dye, a phthalocyanine dye, or a metal complex dye, more preferably cyanide dye. Dyes and merocyanine dyes, arylidene dyes, oxonol dyes, squarylium dyes, azo dyes or phthalocyanine dyes, still more preferred are cyanine dyes, merocyanine dyes or oxonol dyes, and most preferably a cyanine dye.

  For more information on these dyes, see F.M. Harmer, “Heterocyclic Compounds-Cyanine Dies and Related Compounds”, John. John Wiley & Sons-New York, London, 1964, by DM Sturmer, “Heterocyclic Compounds in Special Topics in Heterocyclics” Chemistry (Heterocyclic Compounds-Special topics in heterochemical chemistry) , Chapter 14, Section 14, 482-515, John Wiley & Sons-New York, London, 1977, "Rods Chemistry of Carbon Compounds (Rodd ' s Chemistry of Carbon Compounds) "2nd. Ed. vol. IV, part B, 1977, Chapter 15, pages 369-422, published by Elsevier Science Publishing Company Inc., New York, and the like.

  Specific examples of the cyanine dye, merocyanine dye, or oxonol dye include F.I. M.M. As described by Harmer, Heterocyclic Compounds-Cyanine Dies and Related Compounds, John & Wiley & Sons, New York, London, 1964.

  The general formulas of cyanine dye and merocyanine dye are those shown in (XI) and (XII) on pages 21 and 22 of US Pat. No. 5,340,694 (however, the numbers of n12 and n15 are not limited, An integer of 0 or more (preferably an integer of 0 to 4) is preferable.

  When the non-resonant multiphoton absorption compound of the present invention is a cyanine dye, it is preferably represented by the general formula (3).

In general formula (3), Za1 (in this specification, etc., all superscripts and subscripts in chemical formulas are displayed in full-width. For example, “ ₁ ” and “ ¹ ” are displayed as “1”. ) And Za2 each represents an atomic group forming a 5-membered or 6-membered nitrogen-containing heterocycle. The 5-membered or 6-membered nitrogen-containing heterocycle formed is preferably an oxazole nucleus having 3 to 25 carbon atoms (hereinafter referred to as C number) (for example, 2-3-methyloxazolyl, 2-3-ethyloxazolyl). , 2-3,4-diethyloxazolyl, 2-3-methylbenzoxazolyl, 2-3-ethylbenzoxazolyl, 2-3-sulfoethylbenzoxazolyl, 2-3-sulfopropyl Benzoxazolyl, 2-3-methylthioethylbenzoxazolyl, 2-3-methoxyethylbenzoxazolyl, 2-3-sulfobutylbenzoxazolyl, 2-3-methyl-β-naphthoxazolyl 2-3-methyl-α-naphthoxazolyl, 2-3-sulfopropyl-β-naphthoxazolyl, 2-3-sulfopropyl-β-naphthoxazolyl, 2-3- ( -Naphthoxyethyl) benzoxazolyl, 2-3,5-dimethylbenzoxazolyl, 2-6-chloro-3-methylbenzoxazolyl, 2-5-bromo-3-methylbenzoxazolyl, 2- 3-ethyl-5-methoxybenzoxazolyl, 2-5-phenyl-3-sulfopropylbenzoxazolyl, 2-5- (4-bromophenyl) -3-sulfobutylbenzoxazolyl, 2-3 -Dimethyl-5,6-dimethylthiobenzoxazolyl), thiazole nuclei having 3 to 25 carbon atoms (for example, 2-methylthiazolyl, 2-3-ethylthiazolyl, 2-3-sulfopropylthiazolyl, 2- 3-sulfobutylthiazolyl, 2-3,4-dimethylthiazolyl, 2-3,4,4-trimethylthiazolyl, 2-3-carboxyethylthiazolyl, 2 -3-methylbenzothiazolyl, 2-3-ethylbenzothiazolyl, 2-3-butylbenzothiazolyl, 2-3-sulfopropylbenzothiazolyl, 2-3-sulfobutylbenzothiazolyl , 2-3-methyl-β-naphthothiazolyl, 2-3-sulfopropyl-γ-naphthothiazolyl, 2-3- (1-naphthoxyethyl) benzothiazolyl, 2-3,5-dimethylbenzothiazolyl, 2-6-chloro -3-methylbenzothiazolyl, 2-6-iodo-3-ethylbenzothiazolyl, 2-5-bromo-3-methylbenzothiazolyl, 2-3-ethyl-5-methoxybenzothiazolyl 2-5-phenyl-3-sulfopropylbenzothiazolyl, 2-5- (4-bromophenyl) -3-sulfobutylbenzothiazolyl, 2-3-dimethyl-5,6- Dimethylthiobenzothiazolyl), imidazole nucleus having 3 to 25 carbon atoms (for example, 2-1,3-diethylimidazolyl, 2-1,3-dimethylimidazolyl, 2-1-methylbenzimidazolyl, 2- 1,3,4-triethylimidazolyl, 2-1,3-diethylbenzimidazolyl, 2-1,3,5-trimethylbenzimidazolyl, 2-6-chloro-1,3-dimethylbenzimidazolyl, 2-5,6-dichloro- 1,3-diethylbenzimidazolyl, 2-1,3-disulfopropyl-5-cyano-6-chlorobenzimidazolyl, etc.), C10-30 indolenine nucleus (for example, 3,3-dimethylindolenine) ), A quinoline nucleus having 9 to 25 carbon atoms (for example, 2-1-methylquinolyl, 2-1-ethylquinolyl) 2-1-methyl 6-chloroquinolyl, 2-1,3-diethylquinolyl, 2-1-methyl-6-methylthioquinolyl, 2-1-sulfopropylquinolyl, 4-1-methylquinolyl, 4-1 And sulfoethylquinolyl, 4-1-methyl-7-chloroquinolyl, 4-1,8-diethylquinolyl, 4-1-methyl-6-methylthioquinolyl, 4-1-sulfopropylquinolyl, etc.) , A C 3-25 selenazole nucleus (for example, 2-3methylbenzoselenazolyl etc.), a C 5-25 pyridine nucleus (for example, 2-pyridyl etc.) and the like can be mentioned. In addition, thiazoline nucleus, oxazoline nucleus, selenazoline nucleus, tellurazoline nucleus, tellurazole nucleus, benzotelrazole nucleus, imidazoline nucleus, imidazo [4,5-quino Zarin] nucleus, an oxadiazole nucleus, a thiadiazole nucleus, mention may be made of a tetrazole nucleus or a pyrimidine nucleus.

  These may be substituted, and the substituent is preferably, for example, an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, benzyl, 3- Sulfopropyl, 4-sulfobutyl, carboxymethyl, 5-carboxypentyl), alkenyl group (preferably having 2 to 20 carbon atoms, such as vinyl, allyl, 2-butenyl, 1,3-butadienyl), cycloalkyl group (preferably C 3-20, for example cyclopentyl, cyclohexyl), aryl groups (preferably C 6-20, for example phenyl, 2-chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, 1-naphthyl), heterocyclic groups ( Preferably C number 1-20, for example pyridyl, thienyl, furyl, thiazolyl, imida Lyl, pyrazolyl, pyrrolidino, piperidino, morpholino), alkynyl group (preferably having 2 to 20 carbon atoms, such as ethynyl, 2-propynyl, 1,3-butadiynyl, 2-phenylethynyl), halogen atom (for example, F, Cl Br, I), amino group (preferably C 0-20, for example, amino, dimethylamino, diethylamino, dibutylamino, anilino), cyano group, nitro group, hydroxyl group, mercapto group, carboxyl group, sulfo group, Phosphonic acid group, acyl group (preferably C 1-20, such as acetyl, benzoyl, salicyloyl, pivaloyl), alkoxy group (preferably C 1-20, such as methoxy, butoxy, cyclohexyloxy), aryloxy group (Preferably C number 6-26, for example, phenoxy, 1 Naphthoxy), alkylthio group (preferably C number 1-20, for example, methylthio, ethylthio), arylthio group (preferably C number 6-20, for example, phenylthio, 4-chlorophenylthio), alkylsulfonyl group (preferably C number) 1-20, such as methanesulfonyl, butanesulfonyl), arylsulfonyl groups (preferably C number 6-20, such as benzenesulfonyl, paratoluenesulfonyl), sulfamoyl groups (preferably C number 0-20, such as sulfamoyl, N-methylsulfamoyl, N-phenylsulfamoyl), carbamoyl group (preferably having 1 to 20 carbon atoms, for example, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-phenylcarbamoyl), acylamino group (Preferably C number 1 -20, such as acetylamino, benzoylamino), imino group (preferably C 2-20, such as phthalimino), acyloxy group (preferably C 1-20, such as acetyloxy, benzoyloxy), alkoxycarbonyl group (preferably Is C 2-20, such as methoxycarbonyl, phenoxycarbonyl), carbamoylamino group (preferably C 1-20, such as carbamoylamino, N-methylcarbamoylamino, N-phenylcarbamoylamino), more preferably Is an alkyl group, aryl group, heterocyclic group, halogen atom, cyano group, carboxyl group, sulfo group, alkoxy group, sulfamoyl group, carbamoyl group, or alkoxycarbonyl group.

  These heterocycles may be further condensed. Preferred examples of the condensed ring include a benzene ring, a benzofuran ring, a pyridine ring, a pyrrole ring, an indole ring, and a thiophene ring.

More preferably, the 5-membered or 6-membered nitrogen-containing heterocycle formed by Za1 and Za2 is an oxazole nucleus, an imidazole nucleus, a thiazole nucleus, an indolenine ring, and more preferably an oxazole nucleus, an imidazole nucleus, or an indolenine ring. And most preferably an oxazole nucleus.

  Ra1 and Ra2 each independently represent a hydrogen atom or an alkyl group (preferably having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, benzyl, 3-sulfopropyl, 4 -Sulfobutyl, 3-methyl-3-sulfopropyl, 2'-sulfobenzyl, carboxymethyl, 5-carboxypentyl), alkenyl group (preferably C2-20, for example, vinyl, allyl), aryl group (preferably C number 6-20, for example, phenyl, 2-chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, 1-naphthyl) or a heterocyclic group (preferably C number 1-20, for example pyridyl, thienyl, furyl, Thiazolyl, imidazolyl, pyrazolyl, pyrrolidino, piperidino, morpholino) and more preferred Properly is an alkyl group (preferably an alkyl group having a C number of 1 to 6) or a sulfoalkyl group (preferably 3-sulfopropyl, 4-sulfobutyl, 3-methyl-3-sulfopropyl, 2'-sulfobenzyl).

Ma1 to Ma7 each represents a methine group and may have a substituent (examples of preferred substituents are the same as the examples of substituents on Za1 and Za2), and the substituents are preferably alkyl groups, halogen atoms, A nitro group, an alkoxy group, an aryl group, a nitro group, a heterocyclic group, an aryloxy group, an acylamino group, a carbamoyl group, a sulfo group, a hydroxy group, a carboxy group, an alkylthio group, a cyano group and the like are preferable, and a substituent is more preferable. Is an alkyl group.
Ma1 to Ma7 are preferably an unsubstituted methine group or an alkyl group (preferably having a C number of 1 to 6) substituted methine group, and more preferably an unsubstituted, ethyl group-substituted, or methyl group-substituted methine group.
Ma1 to Ma7 may be linked to each other to form a ring, and preferred examples of the ring formed include a cyclohexene ring, a cyclopentene ring, a benzene ring, and a thiophene ring.

  na1 and na2 are 0 or 1, preferably both 0.

ka1 represents an integer of 0 to 3, more preferably ka1 represents 1 to 3, and further preferably ka1 represents 1 or 2.
When ka1 is 2 or more, the plurality of Ma3 and Ma4 may be the same or different.

  CI represents an ion for neutralizing the electric charge, and y represents a number necessary for neutralizing the electric charge.

  When the nonresonant multiphoton absorption compound of the present invention is a merocyanine dye, it is preferably represented by the general formula (4).

  In the general formula (4), Za3 represents an atomic group forming a 5-membered or 6-membered nitrogen-containing heterocycle (preferred examples are the same as Za1 and Za2), and these may be substituted (examples of preferred substituents). Are the same as the examples of the substituents on Za1 and Za2, and these heterocyclic rings may be further condensed.

  The 5-membered or 6-membered nitrogen-containing heterocyclic ring formed by Za3 is more preferably an oxazole nucleus, an imidazole nucleus, a thiazole nucleus, or an indolenine ring, and more preferably an oxazole nucleus or an indolenine ring.

Za4 represents an atomic group forming a 5-membered or 6-membered ring. The ring formed from Za4 is a part generally called an acidic nucleus, and is defined by James ed., The Theory of the Photographic Process, 4th edition, Macmillan, 1977, p. 198. As Za4, 2-pyrazolone-5-one, pyrazolidine-3,5-dione, imidazolin-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidine-4-one, 2-oxazoline-5 -One, 2-thiooxazoline-2,4-dione, isorhodanine, rhodanine, indan-1,3-dione, thiophen-3-one, thiophen-3-one-1,1-dioxide, indoline-2-one, Indoline-3-one, 2-oxoindazolium, 5,7-dioxo-6,7-dihydrothiazolo [3,2-a] pyrimidine, 3,4-dihydroisoquinolin-4-one, 1,3- Dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid, coumarin-2,4-dione, indazoline-2- Examples include nuclei such as on, pyrido [1,2-a] pyrimidine-1,3-dione, pyrazolo [1,5-b] quinazolone, pyrazolopyridone.
More preferably, the ring formed from Za4 is 2-pyrazolone-5-one, pyrazolidine-3,5-dione, rhodanine, indan-1,3-dione, thiophen-3-one, thiophen-3-one-1. , 1-dioxide, 1,3-dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid, coumarin-2,4-dione, more preferably pyrazolidine-3,5-dione, indane 1,3-dione, 1,3-dioxane-4,6-dione, barbituric acid, or 2-thiobarbituric acid, most preferably pyrazolidine-3,5-dione, barbituric acid, or 2 -Thiobarbituric acid.

  The ring formed from Za4 may be substituted (preferred examples of the substituent are the same as the examples of the substituent on Za3). More preferably, the substituent is preferably an alkyl group, an aryl group, a heterocyclic group, a halogen atom, A cyano group, a carboxyl group, a sulfo group, an alkoxy group, a sulfamoyl group, a carbamoyl group, or an alkoxycarbonyl group.

  These heterocycles may be further condensed. Preferred examples of the condensed ring include a benzene ring, a benzofuran ring, a pyridine ring, a pyrrole ring, an indole ring, and a thiophene ring.

  Each of Ra3 is independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group (preferred examples are the same as Ra1 and Ra2), more preferably an alkyl group (preferably having 1 to 6 carbon atoms). Alkyl group) or a sulfoalkyl group (preferably 3-sulfopropyl, 4-sulfobutyl, 3-methyl-3-sulfopropyl, 2′-sulfobenzyl).

Ma8 to Ma11 each represents a methine group and may have a substituent (examples of preferred substituents are the same as those of the substituents on Za1 and Za2), and the substituents are preferably alkyl groups, halogen atoms, A nitro group, an alkoxy group, an aryl group, a nitro group, a heterocyclic group, an aryloxy group, an acylamino group, a carbamoyl group, a sulfo group, a hydroxy group, a carboxy group, an alkylthio group, a cyano group and the like are preferable, and a substituent is more preferable. Is an alkyl group.
Ma8 to Ma11 are preferably unsubstituted methine groups or alkyl groups (preferably having a C number of 1 to 6) substituted methine groups, more preferably unsubstituted, ethyl group-substituted, or methyl group-substituted methine groups.
Ma8 to Ma11 may be linked to each other to form a ring, and preferred examples of the ring formed include a cyclohexene ring, a cyclopentene ring, a benzene ring, and a thiophene ring.

  na3 is 0 or 1, preferably 0.

ka2 represents an integer of 0 to 8, preferably an integer of 0 to 4, more preferably an integer of 2 to 4.
When ka2 is 2 or more, the plurality of Ma10 and Ma11 may be the same or different.

  CI represents an ion for neutralizing the electric charge, and y represents a number necessary for neutralizing the electric charge.

  When the non-resonant multiphoton absorption compound of the present invention is an oxonol dye, it is preferably represented by the general formula (5).

In the general formula (5), Za5 and Za6 each represent a group of atoms forming a 5-membered or 6-membered ring (preferred examples are the same as Za4), and these may be substituted (examples of preferred substituents are the same as those on Za4). These heterocyclic rings may be further condensed.
More preferably as a ring formed from Za5 and Za6, 2-pyrazolone-5-one, pyrazolidine-3,5-dione, rhodanine, indan-1,3-dione, thiophen-3-one, thiophen-3-one -1,1-dioxide, 1,3-dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid, or coumarin-2,4-dione, more preferably barbituric acid, or 2- Thiobarbituric acid, most preferably barbituric acid.

Ma12 to Ma14 each represent a methine group and may have a substituent (preferred examples of the substituent are the same as the examples of the substituent on Za5 and Za6), and the substituent is preferably an alkyl group or a halogen atom. Nitro group, alkoxy group, aryl group, nitro group, heterocyclic group, aryloxy group, acylamino group, carbamoyl group, sulfo group, hydroxy group, carboxy group, alkylthio group, cyano group, etc., more preferably alkyl Group, a halogen atom, an alkoxy group, an aryl group, a heterocyclic group, a carbamoyl group, or a carboxy group, and more preferably an alkyl group, an aryl group, or a heterocyclic group.
Ma12 to Ma14 are preferably unsubstituted methine groups.
Ma12 to Ma14 may be linked to each other to form a ring, and preferred examples of the ring formed include a cyclohexene ring, a cyclopentene ring, a benzene ring, and a thiophene ring.

ka3 represents an integer from 0 to 3, preferably represents an integer from 0 to 2, more preferably represents 1 or 2, and most preferably represents 2.
When ka3 is 2 or more, Ma12 and Ma13 may be the same or different.

  CI represents an ion for neutralizing the electric charge, and y represents a number necessary for neutralizing the electric charge.

  Moreover, it is also preferable that the compound of this invention is represented by General formula (1).

In the general formula (1), R 1, R 2, R 3 and R 4 each independently represent a hydrogen atom or a substituent, and the substituent is preferably an alkyl group (preferably having a C number of 1 to 20, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, benzyl, 3-sulfopropyl, 4-sulfobutyl, 3-methyl-3-sulfopropyl, 2′-sulfobenzyl, carboxymethyl, 5-carboxypentyl), alkenyl A group (preferably having 2 to 20 carbon atoms, such as vinyl, allyl), a cycloalkyl group (preferably having 3 to 20 carbon atoms, such as cyclopentyl, cyclohexyl), an aryl group (preferably having 6 to 20 carbon atoms, such as phenyl, 2-chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, 1-naphthyl), or a heterocyclic group (Preferably having 1 to 20 carbon atoms, such as pyridyl, thienyl, furyl, thiazolyl, imidazolyl, pyrazolyl, pyrrolidino, piperidino, morpholino).
R1, R2, R3 and R4 are preferably a hydrogen atom or an alkyl group. Some (preferably two) of R1, R2, R3 and R4 may be bonded to each other to form a ring. In particular, R1 and R3 are preferably bonded to form a ring, and the ring formed with the carbonyl carbon atom is preferably a 6-membered ring, a 5-membered ring or a 4-membered ring, and a 5-membered ring or 4-membered ring A ring is more preferable, and a 5-membered ring is most preferable.

In General formula (1), n and m represent the integer of 0-4 each independently, Preferably the integer of 1-4 is represented. However, n and m are not 0 simultaneously.
When n and m are 2 or more, a plurality of R1, R2, R3 and R4 may be the same or different.

  X1 and X2 are independently an aryl group [preferably having 6 to 20 carbon atoms, preferably a substituted aryl group (for example, a substituted phenyl group, a substituted naphthyl group, and preferably the same as the substituents of Ma1 to Ma7 as examples of the substituent). More preferably represents an alkyl group, an aryl group, a heterocyclic group, a halogen atom, an amino group, a hydroxyl group, an alkoxy group, an aryloxy group, an aryl group substituted by an acylamino group, more preferably an alkyl group, an amino group, An aryl group substituted with a hydroxyl group, an alkoxy group, or an acylamino group, and most preferably a phenyl group substituted with a dialkylamino group or a diarylamino group at the 4-position. At that time, a plurality of substituents may be linked to form a ring, and a preferred ring formed includes a julolidine ring. ], A heterocyclic group (preferably having 1 to 20 carbon atoms, preferably 3 to 8 membered ring, more preferably 5 or 6 membered ring such as pyridyl, thienyl, furyl, thiazolyl, imidazolyl, pyrazolyl, pyrrolyl, indolyl, carbazolyl, Phenothiazino, pyrrolidino, piperidino, morpholino, more preferably indolyl, carbazolyl, pyrrolyl, phenothiazino, the heterocycle may be substituted, and preferred substituents are the same as in the case of the aryl group), or the general formula (2) Represents a group represented by

In general formula (2), R5 represents a hydrogen atom or a substituent (preferred examples are the same as R1 to R4), preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.
R6 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group (preferable examples of these substituents are the same as R1 to R4), preferably an alkyl group (preferably an alkyl having 1 to 6 carbon atoms). Group).

Z1 represents an atomic group forming a 5- or 6-membered ring.
The heterocycle formed is preferably an indolenine ring, azaindolenine ring, pyrazoline ring, benzothiazole ring, thiazole ring, thiazoline ring, benzoxazole ring, oxazole ring, oxazoline ring, benzimidazole ring, imidazole ring, thiadiazole ring Quinoline ring, pyridine ring, more preferably indolenine ring, azaindolenine ring, pyrazoline ring, benzothiazole ring, thiazole ring, thiazoline ring, benzoxazole ring, oxazole ring, oxazoline ring, benzimidazole ring, thiadiazole ring A quinoline ring, most preferably an indolenine ring, an azaindolenine ring, a benzothiazole ring, a benzoxazole ring, or a benzimidazole ring.
The heterocycle formed by Z1 may have a substituent (examples of preferred substituents are the same as the examples of substituents on Za1 and Za2), and more preferably alkyl groups, aryl groups, heterocycles as substituents. A ring group, a halogen atom, a carboxyl group, a sulfo group, an alkoxy group, a carbamoyl group, or an alkoxycarbonyl group.

  X1 and X2 are each preferably an aryl group or a group represented by the general formula (2), more preferably an aryl group substituted with a dialkylamino group or a diarylamino group at the 4-position, or a general formula (2). Represented by a group.

The non-resonant multiphoton absorption compound of the present invention preferably has a hydrogen bonding group in the molecule. Here, the hydrogen-bonding group represents a group that donates hydrogen or a group that accepts hydrogen in a hydrogen bond, and a group having both properties is more preferable.
Further, the compound having a hydrogen bonding group of the present invention preferably has an associative interaction by the interaction between hydrogen bonding groups in a solution or in a solid state, and may be an intramolecular interaction or an intermolecular interaction. The interaction is more preferable.

The hydrogen bonding group of the present invention, preferably, -COOH, -CONHR11, -SO3H, -SO 2 NHR12, -P (O) (OH) OR13, -OH, -SH, -NHR14, -NHCOR15, - It is represented by any one of NR16C (O) NHR17. Here, R11 and R12 are each independently a hydrogen atom or an alkyl group (preferably having a carbon atom number (hereinafter referred to as C number) of 1 to 20, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl. Benzyl, 3-sulfopropyl, 4-sulfobutyl, carboxymethyl, 5-carboxypentyl), an alkenyl group (preferably having 2 to 20 carbon atoms, for example, vinyl, allyl), an aryl group (preferably having 6 to 20 carbon atoms, For example, phenyl, 2-chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, 1-naphthyl), a heterocyclic group (preferably having 1 to 20 carbon atoms, such as pyridyl, thienyl, furyl, thiazolyl, imidazolyl, pyrazolyl, pyrrolidino , piperidino, morpholino), - represents COR18 or -SO ₂ R19, R1 ~R19 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group (preferred examples of these R11, the same as R12).

Preferably a hydrogen atom R11, an alkyl group, an aryl group, an -COR18 group -SO ₂ R19 groups. In that case, R18 and R19 are preferably an alkyl group or an aryl group.
R11 is more preferably a hydrogen atom, an alkyl group, or a —SO ₂ R19 group, and most preferably a hydrogen atom.
Preferably a hydrogen atom R12, an alkyl group, an aryl group, an -COR18 group -SO ₂ R19 groups. In that case, R18 and R19 are preferably an alkyl group or an aryl group.
R12 is more preferably a hydrogen atom, an alkyl group or a —COR18 group, and most preferably a hydrogen atom.
R13 preferably represents a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom.
R14 preferably represents a hydrogen atom, an alkyl group or an aryl group.
R15 preferably represents an alkyl group or an aryl group.
R16 preferably represents a hydrogen atom, and R17 preferably represents a hydrogen atom, an alkyl group, or an aryl group.

Hydrogen bonding group is more _{preferably, -COOH, -CONHR11, -SO 2 NHR12} , -NHCOR15, are either -NR16C (O) NHR17, either more preferably -COOH, -CONHR11, a -SO ₂ NHR12 Most preferably, it is either —COOH or —CONH ₂ .

The non-resonant multiphoton absorption compound of the present invention may be used in a monomer state or in an associated state.
Here, the dye chromophores are fixed in a specific spatial arrangement by a bond such as a covalent bond or a coordinate bond, or various intermolecular forces (hydrogen bond, van der Waals force, Coulomb force, etc.) This state is generally referred to as an association (or aggregation) state.
The non-resonant multiphoton absorption compound of the present invention has two or more chromophores that perform non-resonant multiphoton absorption even when used in an intermolecular association state. You may use in the state which absorbs.

For reference, the meeting is explained below. As for the association, for example, James, “The Theory of the Photographic Process”, 4th edition, Macmillan Publishers, 1977, Chapter 8, 218. Pp. 222 and “J-Aggregates” written by Takabayashi Kobayashi, World Scientific Publishing Co. Pte. Ltd., published in 1996). .
A monomer means a monomer. From the viewpoint of the absorption wavelength of the aggregate, the aggregate whose absorption shifts to a short wavelength with respect to monomer absorption is defined as an H aggregate (the dimer is specially called a dimer), and the aggregate whose shift is shifted to a long wavelength. Called coalescence.

  From the viewpoint of the structure of the aggregate, in a brick-stacked aggregate, when the deviation angle of the aggregate is small, it is called a J aggregate, but when the deviation angle is large, it is called an H aggregate. Brickwork aggregates are described in detail in Chemical Physics Letters, Vol. 6, page 183 (1970). In addition, there is a ladder or staircase aggregate as an aggregate having a structure similar to that of a brickwork aggregate. Ladder or staircase structures are described in detail in Zeitschiff for Physikaliche Chemie, Vol. 49, p. 324 (1941).

Moreover, as what forms other than a brickwork aggregate | assembly, the aggregate | assembly (it can call an arrowhead aggregate | assembly) etc. which take an arrow (Herringbone) structure etc. are known.
The Herringbone association is described in Charles Reich, Photographic Science and Engineering, Vol. 18, No. 3, p. 335 (1974). Has been. The arrowhead aggregate has two absorption maxima derived from the aggregate.

Whether or not it is in an associated state can be confirmed by a change in absorption (absorption λmax, ε, absorption type) from the monomer state as described above.
The compound of the present invention may be either short-wavelength (H-association) or long-wavelength (J-association) or both by association, but it is more preferable to form a J-aggregate.

The intermolecular association state of a compound can be formed in various ways.
For example, in a solution system, an aqueous solution to which a matrix such as gelatin is added (for example, gelatin 0.5 wt% / compound 10 ⁻⁴ M aqueous solution), an aqueous solution to which a salt such as KCl is added (for example, KCl 5% · compound 2 × 10 ^−3). M aqueous solution), a method of dissolving a compound in a good solvent, a method of adding a poor solvent afterwards (for example, DMF-water system, chloroform-toluene system, etc.) and the like.
Examples of the film system include polymer dispersion systems, amorphous systems, crystal systems, and LB film systems.
Furthermore, molecules can be adsorbed, chemically bonded, or self-assembled into bulk or fine particle (μm to nm size) semiconductors (eg, silver halide, titanium oxide, etc.), bulk or fine particle metals (eg, gold, silver, platinum, etc.). Inter-association states can also be formed. Spectral sensitization by cyanine dye J-associative adsorption on silver halide crystals in a color silver salt photograph utilizes this technique.
The number of compounds involved in the intermolecular association may be two or a very large number of compounds.

  Although the preferable specific example of the nonresonant multiphoton absorption compound used by this invention is given to the following, this invention is not limited to these.

  As described above, the non-resonant multiphoton absorption compound of the present invention is preferably a non-resonant two-photon absorption compound. In the following description, multiphoton absorption refers to non-resonant multiphoton absorption even if not particularly specified. The multiphoton absorption compound of the present invention functions as a sensitizing dye or functions as a luminescent dye. The function as a sensitizing dye means that the dye that has absorbed light has a function of causing a sensitizing reaction at a quantum yield of 0.01% or more, preferably a quantum yield of 0.1% or more, more preferably 1% or more.

When the nonresonant multiphoton absorption compound of the present invention is a nonresonant multiphoton absorption compound that functions as a sensitizing dye by nonresonant multiphoton absorption, the sensitization mechanism is preferably an energy transfer mechanism or an electron transfer mechanism.
In the case of an energy transfer mechanism, energy transfer occurs from a triplet excited state even in a Forster type mechanism in which energy transfer occurs from a singlet excited state caused by nonresonant multiphoton absorption by a nonresonant multiphoton absorbing compound. Either Dexter type mechanism may be used.
In that case, in order for energy transfer to occur efficiently, the excitation energy of the nonresonant multiphoton absorption compound is preferably larger than the excitation energy of the energy acceptor at the time of sensitization.

On the other hand, in the case of an electron transfer mechanism, the excited state of the nonresonant multiphoton absorption compound may give electrons or receive electrons.
When electrons are supplied from the excited state of the nonresonant multiphoton absorbing compound, the orbital (LUMO) energy in which the excited electron exists in the excited state of the nonresonant multiphoton absorbing compound is used for sensitization in order for the electron transfer to occur efficiently. It is preferably higher than the LUMO orbital energy of the electron acceptor.
When the excited state of the nonresonant multiphoton absorption compound receives electrons, the electron orbit (HOMO) energy in the excited state of the nonresonant multiphoton absorption compound has an orbital (HOMO) energy at the time of sensitization. It is preferably lower than the energy of the HOMO orbital of the electron donor.

  In the non-resonant multi-photon absorption compound that functions as a sensitizing dye by non-resonant multi-photon absorption of the present invention, the non-resonant multi-photon absorption compound absorbs the multi-photon, thereby polymerizing, reacting, coloring, refractive index modulation, light emission. Sensitizing any one of the above, more preferably sensitizing any one of color development, refractive index modulation and light emission, more preferably sensitizing the color development and refractive index modulation, and sensitizing the refractive index modulation. Most preferably.

  When the nonresonant multiphoton absorption compound of the present invention sensitizes polymerization by nonresonant multiphoton absorption, the polymerization may be any of radical polymerization, anionic polymerization, cationic polymerization, condensation polymerization, addition polymerization, ring-opening polymerization and the like. Preferred examples and combinations of polymerization initiators, polymerizable compounds (monomers, oligomers), binders and the like include those described in Japanese Patent Application Nos. 2003-82730 and 2003-82732.

When the nonresonant multiphoton absorption compound of the present invention sensitizes the reaction by nonresonant multiphoton absorption, the reaction is preferably covalent bond formation, covalent bond cleavage, ring closure reaction, ring opening reaction, coordination bond formation, coordination. Examples of functions that occur as a result of positional bond cleavage, oxidation reaction, reduction reaction, etc. are preferably release of functional materials (eg, dyes, illuminants, labeling compounds, pharmacologically active compounds), dye decolorization, compound decomposition, electrolysis Examples include chromic reactions (organic dyes or inorganic semiconductors).
Moreover, as a preferable example when the nonresonant multiphoton absorption compound of the present invention sensitizes the reaction by nonresonant multiphoton absorption, those described in Japanese Patent Application No. 2003-149285 and the like can be mentioned.

When the non-resonant multiphoton absorption compound of the present invention sensitizes color development by non-resonant multiphoton absorption, the color development is preferably a coloration of a leuco dye or the like by acid generation by sensitization, or a dissociation type by base generation by sensitization. Examples include coloring of dyes, coloring of dye precursors by bond cleavage by sensitization, coloring of photochromic compounds by energy transfer sensitization, coloring of electrochromic compounds by electron transfer sensitization, and the like.
Further, as preferred combinations when the non-resonant multiphoton absorption compound of the present invention sensitizes color development by non-resonant multiphoton absorption, Japanese Patent Application Nos. 2003-149285, 2003-184932, and 2003-187258 are disclosed. And the like described in.

The refractive index usually takes a very large value on the long wavelength side of dye absorption. Therefore, it can be said that the refractive index modulation is synonymous with hue modulation, that is, color development reaction.
Therefore, when the nonresonant multiphoton absorption compound of the present invention sensitizes the refractive index modulation by nonresonant multiphoton absorption, the refractive index modulation is preferably a refractive index due to color development of a leuco dye or the like due to acid generation by sensitization. Modulation, refractive index modulation by color development of dissociative dyes due to base generation by sensitization, refractive index modulation by color development of dye precursor by bond cleavage by sensitization, refractive index modulation by photochromic compound color development by energy transfer sensitization, electron Examples include refractive index modulation by color development of electrochromic compounds by transfer sensitization.
As preferred combinations when the non-resonant multiphoton absorption compound of the present invention sensitizes the refractive index modulation due to color development by non-resonant multiphoton absorption, Japanese Patent Application No. 2003-149285, Japanese Patent Application No. 2003-184932, Japanese Patent Application No. What is described in 2003-187258 is mentioned.

On the other hand, refractive index modulation can also be performed in a system that does not use color development. In a system using a polymerizable compound (monomer, oligomer), a non-polymerizable or low-polymerizable binder and a polymerization initiator in combination, the refractive index of the polymerizable compound and the binder is changed in advance, so that the non-resonance of the present invention is achieved. Refractive index modulation can be sensitized by nonresonant multiphoton absorption of a multiphoton absorbing compound.
As described above, Japanese Patent Application No. 2003-146527 discloses a preferred combination when the non-resonant multiphoton absorption compound of the present invention sensitizes the refractive index modulation independent of color development by non-resonant multiphoton absorption. And the like.
Furthermore, as a preferable combination of a polymerization initiator, a polymerizable compound (monomer, oligomer) and a binder, the non-resonant multiphoton absorption compound of the present invention is used as a sensitizing dye in a combination preferably used for a so-called hologram recording material application. By doing so, it can be preferably used in the application of the present invention. Preferred combinations of a polymerization initiator, a polymerizable compound (monomer, oligomer) and a binder include, for example, JP-A-6-43634, JP-A-2-3082, JP-A-3-50588, JP-A-5-107999, Examples include those described in Kaihei 8-16078, Special Table 2001-523842, Special Table 11-512847, and the like.

When the nonresonant multiphoton absorption compound of the present invention sensitizes light emission by nonresonant multiphoton absorption, the sensitization is preferably by an energy transfer mechanism, and more preferably by a single polymerization energy transfer mechanism. As the illuminant that undergoes energy transfer, an organic illuminant (preferably so-called “fluorescent compound (dye)”, “chemiluminescent compound (dye)”, “luminescent compound for organic EL (dye)”, “label” It may be a compound known as “compound (pigment)” or the like, or may be an inorganic luminescent material (fine particles or crystalline semiconductor or metal). In this case, even if the emission efficiency of the non-resonant multiphoton absorption compound itself is low, if the non-resonance multiphoton absorption compound has a high multiphoton absorption efficiency, energy transfer efficiency and emission efficiency of the illuminant that receives energy transfer, There is an advantage that light can be emitted with high efficiency by multiphoton absorption.
Preferable examples of the light emitter when the nonresonant multiphoton absorption compound of the present invention sensitizes light emission by nonresonant multiphoton absorption include those described in Japanese Patent Application No. 2003-149285.

When the non-resonant multiphoton absorbing compound of the present invention is a non-resonant multiphoton absorbing compound that functions as a sensitizing dye, the non-resonant multiphoton absorbing compound is a phenylene vinylene dye in terms of multiphoton absorption efficiency and sensitization efficiency. , Diarylethene dyes, spiropyran dyes, fulgide dyes, fluorene dyes, xanthene dyes, coumarin dyes, and perylene dyes are preferable.
The nonresonant multiphoton absorption is preferably nonresonant two-photon absorption.
When the non-resonant two-photon absorption compound of the present invention is a non-resonant two-photon absorption compound that functions as a sensitizing dye, the non-resonant two-photon absorption cross-sectional area (by the method described in Examples below) is 100 GM or more. It is preferable in terms of improving the writing speed and reducing the size and cost of the laser, more preferably 1000 GM or more, and most preferably 10,000 GM or more.
The non-resonant two-photon absorption cross section represents the sensitivity of two-photon absorption and is defined by 1GM = 1 × 10 ⁻⁵⁰ cm ⁴ s / photon.

The nonresonant multiphoton absorbing compound of the present invention is a nonresonant multiphoton absorbing compound characterized by functioning as a luminescent dye. Functioning as a luminescent dye means that when a nonresonant multiphoton absorption emission area of a nonresonant multiphoton absorption compound is measured in a solution having a concentration of 10 ⁻⁴ M, the emission area due to nonresonant multiphoton absorption of the compound R-1 The non-resonant multiphoton absorption emission area is preferably 10 times or more the non-resonance multiphoton absorption emission area of the compound R-1, and is preferably 100 times or more. It preferably has a non-resonant multiphoton absorption emission area. The nonresonant multiphoton absorption is preferably nonresonant two-photon absorption.

When the nonresonant multiphoton absorption compound of the present invention is a nonresonant multiphoton absorption compound that functions as a luminescent dye, the nonresonant multiphoton absorption compound is a phenylene vinylene dye, diarylethene in terms of multiphoton absorption efficiency, light emission efficiency, and the like. A dye other than a dye, a spiropyran dye, a fulgide dye, a porphyrin dye, a styrene dye, a fluorene dye, a xanthene dye, or a stilbazolium dye is preferable.
When the non-resonant two-photon absorption compound of the present invention is a non-resonant two-photon absorption compound that functions as a luminescent dye, the non-resonant two-photon absorption cross-section is 100 GM or more. In view of the above, it is preferably 1000 GM or more, and most preferably 10,000 GM or more.

In the non-resonant multiphoton absorption compound of the present invention and the material using the same, the multiphoton absorption compound induced by irradiating laser light having a wavelength longer than the linear absorption band of the multiphoton absorption compound and having no linear absorption. It is preferable to develop or emit light using photon absorption.
The laser that can be used in the present invention is not particularly limited, and specifically, a solid laser such as Ti-sapphire having an oscillation wavelength near a central wavelength of 1000 nm, a fiber laser, a semiconductor laser having an oscillation wavelength near 780 nm, a solid A laser, a fiber laser, a semiconductor laser or a solid laser having an oscillation wavelength in the range of 620 to 680 nm can be preferably used.
In addition, a YAG / SHG laser having an oscillation wavelength in the visible light region can also be preferably used.
The laser used in the present invention is preferably a pulsed laser, and more preferably a pulsed laser having a half width on the order of picoseconds or femtoseconds.
In addition, in the non-resonant multiphoton absorption coloring material using the compound of the present invention, it is preferable that λmax of the multiphoton coloring body is shorter than the wavelength of the laser beam irradiated, and in the multiphoton absorption light emitting material of the present invention Is preferably shorter than the wavelength of the laser beam with which the emission wavelength of the light emitter is irradiated.
The same applies to the non-resonant two-photon absorption compound.

The non-resonant multiphoton absorption compound of the present invention and a material using the same are a composition for three-dimensional stereolithography, a volume type three-dimensional display, a three-dimensional optical recording medium, two-photon contrast imaging and two-photon photodynamic therapy (PDT) of living tissue. ), Preferably used for application to a wavelength conversion device by up-conversion lasing, and more preferably used for application to a volume type three-dimensional display and a three-dimensional optical recording medium.
[Example]
Hereinafter, specific embodiments of the present invention will be described based on experimental results. Of course, the present invention is not limited to these examples.

  Synthesis of non-resonant multiphoton absorption compounds of the present invention

(1) Synthesis of D-73

  The non-resonant multiphoton absorption compound D-73 of the present invention can be synthesized by the following method.

  14.3 g (40 mmol) of the quaternary salt [1] was dissolved in 50 ml of water, 1.6 g (40 mmol) of sodium hydroxide was added, and the mixture was stirred at room temperature for 30 minutes. The mixture was extracted three times with ethyl acetate, dried over magnesium sulfate and concentrated to obtain 9.2 g (yield 100%) of methylene-based [2] oil.

  3.97 g (40 mmol) of dimethylaminoacrolein [3] was dissolved in 50 ml of acetonitrile, and 6.75 g (44 mmol) of phosphorus oxychloride was added dropwise while cooling to 0 ° C., followed by stirring at 0 ° C. for 10 minutes. Subsequently, 9.2 g of acetonitrile solution of methylene base [2] was dropped, and the mixture was stirred at 35 ° C. for 4 hours. After pouring into 100 ml of ice water, 16 g of sodium hydroxide was added and refluxed for 10 minutes. After cooling, the mixture was extracted 3 times with ethyl acetate, dried over magnesium sulfate and concentrated. Purification by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 10 → 1: 3) gave 4.4 g (39% yield) of aldehyde [4] as an oil.

  0.126 g (1.5 mmol) of cyclopentanone and 0.85 g (3 mmol) of aldehyde [4] were dissolved in 30 ml of dehydrated methanol and refluxed in a dark place under a nitrogen atmosphere. After becoming uniform, 0.69 g (3.6 mmol) of a 28% sodium methoxide methanol solution was added, and the mixture was further refluxed for 6 hours. After cooling, the precipitated crystals were separated by filtration and washed with methanol to obtain 0.50 g (yield 54%) of D-73 dark green crystals. The structure was confirmed by NMR spectrum, MS spectrum and elemental analysis.

(2) Synthesis of D-84

  The non-resonant multiphoton absorption compound D-84 of the present invention can be synthesized by the following method.

  33.6 g (0.4 mol) of cyclopentanone, 2 ml of DBN, and 400 g of N, N-dimethylformamide dimethyl acetal were refluxed for 5 days. After concentration, acetone was added and cooled to separate the crystals, which were then washed with cold acetone to obtain 32.4 g of crystals [5] (yield 42%).

[5] 0.78 g (4 mmol), quaternary salt [6] 2.78 g (8 mmol), and 20 ml of pyridine were refluxed in a dark place under a nitrogen atmosphere for 4 hours. After cooling, ethyl acetate was added and the crystals were separated and washed with ethyl acetate. The crystals were dispersed in methanol and separated by filtration to obtain 2.14 g (yield 56%) of the desired deep blue crystals of D-84.
The structure was confirmed by NMR spectrum, MS spectrum and elemental analysis.

  In addition, other nonresonant multiphoton absorption compounds represented by the general formula (1) of the present invention can be synthesized by the synthesis methods of D-73 and D-84, Tetrahedron. Lett. 42, 6129, (2001) and the like.

(3) Synthesis of D-1

  The nonresonant multiphoton absorption compound D-1 of the present invention can be synthesized by the following method.

  Benzoxazole [7] 52.25 g (0.2 mol) and propane sultone [8] 45.75 g (0.375 mol) were heated and stirred at 140 ° C. for 4 hours. After cooling, acetone was added and the crystals were separated, and washed with acetone to obtain 70.42 g (yield 85%) of a quaternary salt [9].

Quaternary salt [9] 66.2 g (0.2 mol), triethyl orthopropionate [10] 200 ml, pyridine 200 ml and acetic acid 80 ml were heated and stirred at 120 ° C. for 1 hour. After cooling, decantation washing was performed 3 times with ethyl acetate. When dissolved in 100 ml of methanol and stirred, a solution of sodium acetate 4.0 g (50 mmol) / methanol 20 ml was added, and the resulting crystals were separated. Furthermore, it disperse | distributed to methanol and separated and obtained the target D-1 vermilion crystal 31.36g (yield 43.4%).
The structure was confirmed by NMR spectrum, MS spectrum and elemental analysis.

(4) Synthesis of D-42

  The non-resonant multiphoton absorption compound D-42 of the present invention can be synthesized by the following method.

Quaternary salt [11] 2.81 g (10 mmol), [12] 6.67 g (30 mmol), acetic anhydride 10 g, and acetonitrile 50 ml were refluxed for 30 minutes. After concentration, decantation with ethyl acetate was performed to obtain a crude product of anil form [13].
To a crude product of the anil compound [13], 2.00 g (10 mmol) of thiobarbituric acid [14], 3.0 g (30 mmol) of triethylamine and 100 ml of ethanol were added and refluxed for 1 hour. After concentration, the residue was purified by silica gel column chromatography (developing solvent: chloroform: methanol = 20: 1 → 10: 1), and further recrystallized from methanol-isopropyl alcohol to obtain 2.55 g of the target D-42 crystal. (Total yield 41.3%) was obtained.
The structure was confirmed by NMR spectrum, MS spectrum and elemental analysis.

(5) Synthesis of D-56

  The non-resonant multiphoton absorption compound D-56 of the present invention can be synthesized by the following method.

Barbituric acid [15] 3.12 g (20 mmol), [16] 2.85 g (10 mmol) and triethylamine 4.1 g (40 mmol) were dissolved in DMF 30 ml, and the mixture was stirred at room temperature for 2 hours. Crystals produced by adding dilute hydrochloric acid were filtered, washed with water and dried to obtain 2.99 g (yield: 80.0%) of the desired D-56 crystals.
The structure was confirmed by NMR spectrum, MS spectrum and elemental analysis.

  Further, other cyanine dyes, merocyanine dyes, oxonol dyes and the like are also described in F.I. M.M. By Harmer, Heterocyclic Compounds-Cyanine Dies and Related Compounds, John & Wiley & Sons, New York, London, 1964, D.C. M.M. According to Sturmer, Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry, Chapter 18, Section 14, pages 482 to 515, according to John & Wiley & Sons, New Yor et al.

  However, the synthesis method of the non-resonant multiphoton absorption compound of the present invention is not limited to this.

  [Evaluation of non-resonant two-photon absorption cross section]

Next, the nonresonant two-photon absorption cross section of the nonresonant multiphoton absorption compound of the present invention was evaluated.
[1. Fluorescence method]
The evaluation of the non-resonant two-photon absorption cross section is as follows. A. Albota et al. , Appl. Opt. 1998, 37, 7352. The description was made with reference to the method described. A Ti: sapphire pulse laser (pulse width: 100 fs, repetition rate: 80 MHz, average output: 1 W, peak power: 100 kW) is used as a light source for non-resonant two-photon absorption cross-section measurement, and it is not in a wavelength range of 700 nm to 1000 nm. The resonant two-photon absorption cross section was measured. In addition, rhodamine B and fluorescein were measured as reference substances, and the obtained measured values were calculated as C.I. Xu et al. , J. et al. Opt. Soc. Am. B 1996, 13, 481. Were corrected using the values of the non-resonant two-photon absorption cross sections of rhodamine B and fluorescein described in 1. to obtain the non-resonant two-photon absorption cross sections of the respective compounds. As a sample for non-resonant two-photon absorption measurement, a solution in which a compound was dissolved at a concentration of 1 × 10 ⁻⁴ was used. The non-resonant two-photon absorption cross section measurement method is referred to as “fluorescence method” in the present invention.

[2. Z-Scan method]
For compounds that do not fluoresce or are weak, the nonresonant two-photon absorption cross-section is evaluated by MANSOOR SHEIK-BAHAE et al. , IEEE. Journal of Quantum Electronics. 1990, 26, 760. The Z scan method described was used. The Z-scan method is widely used as a method for measuring nonlinear optical constants. The measurement sample is moved along the beam near the focal point of the focused laser beam, and the change in the amount of transmitted light is recorded. . Since the power density of incident light varies depending on the position of the sample, the amount of transmitted light attenuates near the focal point when there is nonlinear absorption. A non-resonant two-photon absorption cross section was calculated by fitting a change in the amount of transmitted light to a theoretical curve predicted from incident light intensity, focused spot size, sample thickness, sample concentration, and the like. A Ti: sapphire pulse laser (pulse width: 100 fs, repetition rate: 80 MHz, average output: 1 W, peak power: 100 kW) is used as a light source for non-resonant two-photon absorption cross section measurement, and non-resonant in a wavelength range of 700 nm to 1000 nm. The resonant two-photon absorption cross section was measured. As a sample for non-resonant two-photon absorption measurement, a solution in which a compound was dissolved at a concentration of 1 × 10 ⁻² was used.
The non-resonant two-photon absorption cross section measurement method is referred to as “Z-Scan method” in the present invention.

The two-photon absorption cross section of the non-resonant two-photon absorption compound of the present invention was measured by either of the above methods, and the obtained results are shown in Table 1 in GM units (1GM = 1 × 10 ⁻⁵⁰ cm ⁴ s). / Photon). The value shown in the table is the maximum value of the non-resonant two-photon absorption cross section within the measurement wavelength range.

  From Table 1, the non-resonant multiphoton absorption compounds D-1 to D-206 that are preferable in the present invention are extremely high non-resonant two-photons compared to the compounds R-1 to R-4 that are not preferable in the present invention. It is clear that the absorption efficiency is shown. Since the sensitization efficiency and the light emission efficiency are proportional to the nonresonant two-photon absorption cross section, it can be seen that the preferred nonresonant multiphoton absorption compound of the present invention can be expected to have very high sensitization efficiency and light emission efficiency.

  [Method for evaluating non-resonant two-photon absorption emission ability]

Next, the non-resonant two-photon absorption emission ability of the non-resonant multiphoton absorption compound that functions as the luminescent dye of the present invention is evaluated.
The solutions of D-42, D-56, D-73, D-77, D-117, D-5, D-128, and R-1 of Example 2 were described in Table 1 using the laser described in Example 2. The emission spectrum obtained by the non-resonant two-photon absorption was measured. The area of the obtained emission spectrum was defined as non-resonant two-photon absorption emission intensity.
The non-resonant two-photon absorption emission intensity is shown in Table 2 as a relative ratio with the value of R-1 being 1.

  From Table 2, it is clear that the non-resonant multiphoton absorption compound preferred in the present invention exhibits extremely high non-resonant two-photon absorption emission efficiency as compared with the compound R-1, which is less preferred in the present invention. Therefore, it is clear that the non-resonant multiphoton absorption compound of the present invention functions as a highly efficient luminescent dye.

[Evaluation of polymerization, color development, refractive index modulation sensitization ability of non-resonant multiphoton absorption compound of the present invention]

  Next, the sensitizing function of the non-resonant multiphoton absorbing compound that functions as the sensitizing dye of the present invention is evaluated. First, evaluation is performed when sensitizing polymerization, color development, and refractive index modulation.

  Preparation of the photosensitive polymer composition of the present invention

Composition Polymer Compound of Photopolymerizable Composition (1): Poly (butyl methacrylate-co-) manufactured by Aldrich
(Isobutyl methacrylate) 100 parts by mass Two-photon absorption compound: D-104 0.5 parts by mass Acid generator: diphenyliodonium tetrafluoroborate 3.0 parts by mass Acid coloring compound: Crystal violet lactone 3.0 parts by mass

Composition Polymer Compound of Photopolymerizable Composition (2): Poly (butyl methacrylate-co-) manufactured by Aldrich
Isobutyl methacrylate) 100 parts by mass Two-photon absorption compound: D-104 0.05 parts by mass Acid generator: 3.0 parts by mass of diphenyliodonium tetrafluoroboric acid Acid coloring compound: 3.0 parts by mass of crystal violet lactone

Composition Polymer Compound of Photopolymerizable Composition (3): Poly (butyl methacrylate-co-) manufactured by Aldrich
Isobutyl methacrylate) 100 parts by mass Two-photon absorption compound: D-104 0.5 parts by mass Acid generator: Diphenyliodonium tetrafluoroboric acid 3.0 parts by mass Coloring compound: Rhodamine B base 3.0 parts by mass

Comparative Example (1)
High molecular compound: Aldrich poly (butyl methacrylate-co-
(Isobutyl methacrylate) 100 parts by mass acid generator: diphenyliodonium tetrafluoroborate 3.0 parts by mass acid coloring compound: crystal violet lactone 3.0 parts by mass

Comparative example (2)
High molecular compound: Aldrich poly (butyl methacrylate-co-
Isobutyl methacrylate) 100 parts by mass Two-photon absorption compound: D-104 0.5 parts by mass Acid generator: diphenyliodonium tetrafluoroborate 3.0 parts by mass

Comparative Example (3)
High molecular compound: Aldrich poly (butyl methacrylate-co-
Isobutyl methacrylate) 100 parts by mass Two-photon absorption compound: 0.5 part by mass of R-4 described in Non-Patent Document 6 In addition, diarylethene R-4 used as the two-photon absorption compound is newly around 520 nm by photochromism by two-photon absorption. It is a compound in which simple absorption appears. The maximum value of the two-photon absorption cross section of the compound is 10GM.

[Performance evaluation]
For the performance evaluation of the photopolymerizable composition of the present invention, the photosensitive polymer composition prepared in each of the above compositions is sandwiched between two cover glasses (thickness: about 100 μm), and non-resonant two-photon absorption is performed. After irradiation with femtosecond laser pulse light having a wavelength corresponding to the two-photon absorption maximum wavelength of the compound, the presence or absence of color formation of the acid coloring dye or the photochromic compound in the light irradiation portion was visually observed. In addition, the intensity | strength and irradiation time of the irradiated laser pulse light were made constant between each composition. The results are shown in Table 3.

From Table 3, the comparative example (1) in which the non-resonant two-photon absorption compound is not present and the comparative example (2) in which the coloring compound is not present are not colored, whereas the compositions (1) to (3) are colored. From this, it is clear that the non-resonant two-photon absorption compound generates acid in the acid generator by the sensitization mechanism after the non-resonant two-photon absorption, thereby causing the coloring compound to develop color.
In addition, even under conditions where the compositions (1) to (3) can develop color, Comparative Example (3) using only the diarylethene R-4 and the polymer compound does not develop color. This is because R-4 has only a very low non-resonant two-photon absorption efficiency of 10GM.
Thus, the preferred non-resonant multiphoton absorption compound in the present invention can cause color development and polymerization with very high efficiency by the sensitization mechanism. This is an extremely effective means when the non-resonant two-photon absorption efficiency of the desired coloring compound or the polymerization initiator itself is not large.
Non-resonant two-photon absorption compounds are D-4, D-5, D-42, D-56, D-73, D-77, D-96, D-101, D-110, D-117, D The same effect can be obtained by changing to other preferable compounds in the present invention such as -118, D-128, D-139, D-140, D-142, D-144, and D-145. Further, when the sensitivity of color development and polymerization is estimated from the irradiation time at which the color development becomes visible, when the preferred non-resonant two-photon absorption compound is used in the present invention, the case where R-2 which is not preferred is used It was found that a much higher sensitivity can be obtained.

  The above-described colored polymer composition can also form a refractive index modulated image due to the difference in refractive index between the colored portion and the non-colored portion, and the refractive index difference at the portion is read by a change in reflectance due to light irradiation. be able to. Therefore, the non-resonant two-photon absorption compound of the present invention can be highly sensitized by refractive index modulation, and can be applied to a three-dimensional optical recording medium and its recording / reproducing method.

[Evaluation of Luminescence Sensitivity of Nonresonant Multiphoton Absorbing Compound of the Present Invention]

  Next, a method for evaluating the luminescence sensitizing ability when the non-resonant multiphoton absorption compound of the present invention generates an excited state by non-resonant two-photon absorption and then transfers energy to the dye precursor to cause the illuminant to emit light. State.

A solution in which non-resonant two-photon absorption compound D-4 was dissolved in methanol at a concentration of 10 ⁻³ M and rhodamine B (R-3) as a light emitter at a concentration of 10 ⁻³ M was prepared in the dark. The sample 201 was spin-coated afterward.
Further, a comparative sample 4 was prepared by spin-coating a solution in which only rhodamine B (R-3) was dissolved in methanol at a concentration of 10 ⁻³ M in the dark.

For the performance evaluation of the non-resonant two-photon absorption luminescent material of the present invention, a Ti: sapphire pulse laser (pulse width: 100 fs, repetition rate: 80 MHz, average output: 1 W, peak power: 100 kW, which can be measured in the wavelength range of 700 nm to 1000 nm. ), The non-resonant two-photon absorption light-emitting material of the present invention was irradiated with the laser beam condensed with a lens having NA of 0.6.
The irradiation wavelength used was a wavelength that maximized the non-resonant two-photon absorption cross section δ in a 10 ⁻⁴ M solution of the two-photon absorption compound. At the irradiation wavelength, there is no linear absorption in either the two-photon absorption compound or the light emitter.
For the sample 201 and the comparative sample 4 of the present invention, the amount of laser irradiation was estimated so that the intensity of the light emitted from the illuminant due to energy transfer from the excited state of the two-photon absorption compound out of the light emitted by the pulse laser irradiation was a certain amount. As a result, it was found that the sample 201 required 1/88 of the irradiation light amount of the comparative sample 4. That is, it was found that the sensitivity was 88 times.

A similar experiment was performed by changing the two-photon absorption compound to D-5, D-41, D-56, D-73, D-77, D-86, D-93, D-117, and D-128. However, similarly, it was found that the sensitivity of the comparative sample 4 was very high.
Thus, the preferred non-resonant two-photon absorption compound in the present invention can cause the luminescent material to emit light very efficiently by the sensitization mechanism. This is a very effective means when the non-resonant two-photon absorption efficiency of the desired light emitter itself is not large.
From the above, it is clear that the non-resonant two-photon absorption compound of the present invention can function as a sensitizing dye or a luminescent dye with extremely high efficiency.

  The non-resonant multiphoton absorption compound of the present invention and a material using the same are a composition for three-dimensional stereolithography, a volume type three-dimensional display, a three-dimensional optical recording medium, two-photon contrast imaging and two-photon photodynamic therapy (PDT) ), And can be used for application to wavelength conversion devices by up-conversion lasing. In addition, application to an optical recording medium such as DVD-BL (BR) or DVD-R or a near-field optical recording medium is also possible.

Claims (7)

A nonresonant multiphoton absorbing material comprising a highly efficient nonresonant multiphoton absorbing compound that functions as a sensitizing dye or a light emitting dye with nonresonant multiphoton absorption. 2. The non-resonant multiphoton absorption compound sensitizes at least one of polymerization, reaction, color development, refractive index modulation, and light emission with high efficiency by absorbing multiphotons non-resonantly. Non-resonant multiphoton absorbing material. The non-resonant two-photon absorption material according to claim 1 or 2, wherein the non-resonant multi-photon absorption compound has a non-resonant two-photon absorption cross section of 1000 GM or more. When the nonresonant multiphoton absorption emission area of the nonresonance multiphoton absorption compound is measured in a solution having a concentration of 10 ⁻⁴ M, the nonresonance multiphoton absorption is 10 times or more the nonresonance multiphoton absorption emission area of the following compound R-1. The nonresonant multiphoton absorption material according to any one of claims 1 to 3, which has a light emitting area.

Non-resonant multiphoton absorption compounds are cyanine dyes, hemicyanine dyes, streptocyanine dyes, styryl dyes, pyrylium dyes, merocyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, rhodacyanine dyes, complex cyanine dyes, complex merocyanine dyes, allopolar dyes. , Arylidene dye, oxonol dye, hemioxonol dye, squalium dye, croconium dye, azurenium dye, ketocoumarin dye, styrylcoumarin dye, pyran dye, anthraquinone dye, quinone dye, triphenylmethane dye, diphenylmethane dye, thioxanthene dye, phenothiazine Dye, Phenoxazine Dye, Phenazine Dye, Azo Dye, Azomethine Dye, Indigo Dye, Polyene Dye, Acridine Dye, Acrid Dye, diphenylamine dye, quinacridone dye, quinophthalone dye, porphyrin dye, azaporphyrin dye, chlorophyll dye, phthalocyanine dye, fused aromatic dye, styrene dye, metallocene dye, metal complex dye, stilbazolium dye The nonresonant multiphoton absorption material according to any one of claims 1 to 4, The nonresonant multiphoton absorbing material according to claim 1, wherein the nonresonant multiphoton absorbing material is used as a three-dimensional stereolithography composition. The nonresonant multiphoton absorbing material according to claim 1, wherein the nonresonant multiphoton absorbing material is used as a three-dimensional display or a three-dimensional optical recording medium.